IE913947A1 - Production of anhydrides and nitriles - Google Patents

Abstract

In order to produce a nitrile or cyclic anhydride derivative of a hydrocarbon, the hydrocarbon is reacted in the vapour phase in the presence of a catalyst with oxygen, and, if a nitrile is to be produced, ammonia in a partial oxidation reactor 2. A gaseous mixture including said derivative, carbon monoxide and carbon dioxide is produced. The derivative is then scrubbed out of the mixture in product removal means 8. Carbon dioxide is separated from the resulting gaseous mixture, preferably by pressure swing adsorption is separator 16. The carbon dioxide depleted gaseous product is recycled to the reactor 2 or its outlet (or both). The process is operated so as to maintain the total concentration of carbon monoxide and hydrocarbon present in all parts of the system sufficiently high (i.e. above the upper explosive limit) to prevent the existence of a flammable mixture in the process.

Description

PRODUCTION OF ANHYDRIDES AND NITRILES The present invention is directed to a process and apparatus for producing a cyclic anhydride or a nitrile from a hydrocarbon and an oxygen-containing gas in the presence of a suitable catalyst, and more particularly to a process for reducing or eliminating the hazard of an explosion or fire in a vapour phase reactor system in which an anhydride or a nitrile is produced from a hydrocarbon and oxygen.

Cyclic anhydrides and a,β-olefinically unsaturated nitriles are produced commercially by the oxidation of appropriate hydrocarbons in the vapour phase over suitable catalysts. For example, maleic anhydride is produced commercially by the vapour phase oxidation of benzene or straight C^ hydrocarbons (hydrocarbons containing four carbon atoms), such as n-butane, butene or butadiene with an oxygen containing gas, over a vanadium-phosphorus oxide catalyst, and acrylonitrile is produced commercially by the vapour phase contacting of propane or propylene with an oxygen-containing gas and ammonia, over a bismuth-molybdenum oxide catalyst. Air is generally used as the oxygen-containing gas, because of its low cost and ready availability. The reaction can be carried out in any suitable reactor, such as a fixed or fluidised bed reactor, and it produces the nitrile, and generally carbon monoxide (CO), carbon dioxide (C02), water, and smaller amounts of other partially oxidised by-products. The reaction equipment train generally consists of a reactor, in which the cyclic anhydride or the nitrile is produced, a scrubber, in which the anhydride or nitrile is scrubbed from the reactor effluent gases by means of water or other solvent for the anhydride or nitrile, and means for further treating the scrubbed effluent gases.

In the past it was common to practise the above-described process on a single pass basis with the conversion of hydrocarbon being maximised.

This resulted in a low overall efficiency, since the selectivity to the anhydride or nitrile was below the maximum. Consequently, the scrubber effluent gas contained, in addition to unreacted hydrocarbon, considerable amounts of CO and C02- These products were usually incinerated, so that the only return realised from them was heat value.

In later processes a portion of the scrubber effluent gas was recycled, 91A210/MW IE 913947 -2the conversion of the hydrocarbon feedstock was lowered and the selectivity of hydrocarbon conversion to anhydride or nitrile was maximised. The remainder of the effluent was purged from the system to prevent the build-up of CO, C02 and nitrogen (introduced into the system when air is used as the source of oxygen). These improvements resulted in a reduced per pass conversion but the overall efficiency of the process was increased.

A major problem associated with the gas phase production of anhydrides and nitriles by the oxidation of hydrocarbons with an oxygen-containing gas is that since the reaction is carried out at elevated temperatures, there is an ever-present danger of a fire or an explosion in the reactor or the equipment or pipelines associated with the reactor as a result of the decomposition of unreacted hydrocarbons. The propensity of the hydrocarbons to decompose is enhanced by the presence of catalyst, and the tendency toward decomposition is particularly enhanced at the outlet of fluidised bed or transport bed reactors. Accordingly, the concentrations of the reactants in the system are maintained such that the mixture is kept outside of the flammability range. Although nitrogen serves to reduce the flammable mixture range when air is used as the source of oxygen for the reaction, the flammable mixture range for hydrocarbon-air mixtures is still quite broad. Consequently, it has been customary to operate gas phase anhydride and nitrile reactors at low hydrocarbon levels so that the reaction mixture will remain outside of the flammable range.

As is well known, under a given set of conditions of temperature and pressure the flammability of a gaseous hydrocarbon-oxygen mixture is dependent upon the ratio of the gaseous components in the mixture. At very low hydrocarbon concentrations the gas mixture is non-flammable, but at a certain hydrocarbon concentration threshold level, usually referred to as the lower explosive limit (LEL), the mixture becomes flammable and remains flammable with increasing hydrocarbon concentrations until the hydrocarbon level reaches a certain level, often referred to as the upper explosive limit (UEL) of the gas mixture. The explosive range of a gaseous fuel-oxygen mixture rapidly expands as the temperature of the system increases. Even though it might otherwise be desirable to operate a gaseous cyclic anhydride or nitrile manufacturing process at 91A210/MW IE 913947 3 hydrocarbon concentrations in the explosive range, it is dangerous to do so because of the hazard of fire or explosion in the reactor or associated equipment. The present invention permits optimisation of the selectivity and yield of the process, even while operating the process at hydrocarbon concentrations normally falling within the flammable mixture range. In the past, this was not considered possible.

According to the present invention there is provided a process for the production of a hydrocarbon derivative selected from cyclic anhydrides and nitriles comprising: (a) contacting in the vapour phase in a reaction zone a hydrocarbon, an oxygen-containing gas and, if the hydrocarbon derivative is a nitrile, ammonia, in the presence of an partial oxidation catalyst and carbon monoxide as the principal gaseous component under conditions which produce a gaseous product containing said hydrocarbon derivative, carbon monoxide and carbon dioxide; (b) recovering said hydrocarbon derivative from said gaseous product; (c) separating carbon dioxide from the gaseous product; and (d) recycling the carbon dioxide-depleted gaseous product to said reaction zone or its outlet (or both), the concentration of carbon monoxide and hydrocarbon present in all parts of the system in which said process is conducted being maintained sufficiently high during said process to prevent the existence of a flammable mixture in said system.

The invention also provides Apparatus for producing a hydrocarbon derivative by the vapour phase partial oxidation of a hydrocarbon with oxygen in the presence of an partial oxidation catalyst comprising: (a) reactor means for oxidising a hydrocarbon with oxygen to produce a gaseous product stream containing said hydrocarbon derivative, carbon monoxide and unreacted hydrocarbon; (b) means for removing hydrocarbon derivative from said gaseous product stream to produce a liquid product stream containing said hydrocarbon derivative and a gas stream, substantially free of said hydrocarbon derivative, containing carbon monoxide and unreacted hydrocarbon; 91A210/MW IE 913947 4 (c) means for separately removing unreacted hydrocarbon and carbon monoxide from said gas stream; (d) means for recycling said separated unreacted hydrocarbon to the upstream side of said reactor means; and (e) means for recycling said separated carbon monoxide to the downstream side of said reactor means.

The carbon dioxide-depleted stream is conveniently recycled to the feed inlet or to the feed outlet of the hydrocarbon oxidation reactor. Unreacted hydrocarbon can be recycled to the feed inlet of the hydrocarbon reactor with the carbon monoxide-rich recycle stream. Alternatively, the unreacted hydrocarbon can be removed from the effluent and recycled to the inlet to the hydrocarbon reactor and the carbon monoxide-rich stream can be recycled to the downstream side of the reactor.

According to one embodiment of the process of the invention, one or more hydrocarbon anhydride or nitrile precursors, such as benzene, orthoxylene, naphthalene, butane or butene, in the case of anhydride production, and propylene or propane, in the case of nitrile production are contacted with an oxygen-containing gas and, where appropriate, ammonia in a suitable partial oxidation reactor and in the presence of carbon monoxide as the principal gaseous component, to produce a gaseous product stream containing a cyclic anhydride, such as maleic anhydride or phthalic anhydride, or a nitrile, such as acrylonitrile or methacrylonitrile, the specific product being produced depending upon which hydrocarbon or hydrocarbons are reacted. The hydrocarbon oxidation reactor product stream also contains carbon monoxide and carbon dioxide, and generally unreacted hydrocarbon(s), oxygen, and possibly small amounts of other reaction by-products. The gaseous product stream leaving the partial oxidation reactor is treated in a cyclic anhydride or nitrile removal means, such as a scrubber in which the anhydride or nitrile is contacted with a liquid solvent which removes substantially all of the product from the gas stream. The anhydride-containing or nitrile-containing liquid is discharged from the product removal means and treated to recover the product. All or a portion of the anhydride-depleted or nitrile-depleted gaseous product stream is then treated in a carbon dioxide separator which removes some or all of the 91A210/MW IE 913947 -5carbon dioxide, and which also removes carbon monoxide in excess of the amount that it is desired to maintain in the system. The remainder of the gaseous effluent, comprises predominantly carbon monoxide and unreacted hydrocarbon, is recycled to the inlet of the hydrocarbon partial oxidation reactor.

In an alternative embodiment of the process of the invention the gaseous effluent from the scrubber is treated in a hydrocarbon separator to remove substantially all of the unreacted hydrocarbon from the scrubbed gas stream and the separated unreacted hydrocarbon is recycled to the hydrocarbon oxidation reactor inlet. All or a portion of the hydrocarbon-depleted effluent from the hydrocarbon separator is then treated in a carbon dioxide separator to remove carbon dioxide and excess carbon monoxide from the stream and the remainder of the stream, now rich in carbon monoxide, is recycled to either the inlet to or the outlet from the hydrocarbon partial oxidation reactor, or to both, if desired.

In a preferred embodiment of the process aspect of the invention the oxygen-containing gas is substantially pure oxygen. In another preferred embodiment carbon dioxide is removed from the scrubber effluent by adsorption, absorption or membrane separation. When the process is used to produce maleic anhydride, the preferred feed hydrocarbons are the four-carbon straight-chain hydrocarbons, and the most preferred straight-chain hydrocarbon is n-butane. Orthoxylene is the preferred hydrocarbon feed for the manufacture of phthalic anhydride by the process of the invention. When the process is used to produce acrylonitrile, the preferred feed hydrocarbons are the three-carbon straight-chain hydrocarbons, and the most preferred straight-chain hydrocarbon is n-propane. Isobutane is the preferred hydrocarbon feed for the manufacture of methacrylonitrile by the process of the invention.

Another novel aspect of the invention is the system in which one embodiment of the process of the invention is carried out. The system comprises a hydrocarbon reactor, a cyclic anhydride or nitrile removal means, an unreacted hydrocarbon separator, a carbon dioxide separator and connecting conduits. The hydrocarbon reactor outlet is connected to the anhydride or nitrile removal means. In turn, the gaseous effluent outlet from the anhydride or nitrile removal means is connected to the inlet to 91A210/MV either the unreacted hydrocarbon separator or the carbon dioxide separator, whichever unit is first in the equipment train. The unreacted hydrocarbon separator and the carbon dioxide separator are arranged serially in the train and either unit may precede the other. The waste gas stream outlet from the last separator in the train is connected to a vent line. In the novel system of the invention the recycle stream line from the unreacted hydrocarbon separator is connected to the inlet to the hydrocarbon reactor and the carbon monoxide recycle stream line from the carbon dioxide separator is connected to the outlet from the hydrocarbon reactor.

The invention is now described by way of example with reference to the accompanying drawings, in which: Fig. 1 illustrates, in a block diagram, one embodiment of a system for producing a cyclic anhydride or a nitrile in accordance with the present invention.

Fig. 2 illustrates, in a block diagram, an alternative embodiment of the system illustrated in Fig. 1.

According to the process of the invention, a hydrocarbon in the gaseous state is reacted with oxygen and, optionally, ammonia in a reaction zone containing a suitable catalyst and in the presence of carbon monoxide as the principal gaseous component to produce a gaseous product stream containing a cyclic anhydride or an a, β-olefinically unsaturated nitrile as the desired product, carbon monoxide and carbon dioxide as by-products and usually unreacted hydrocarbon and oxygen; the petrochemical is recovered from the gaseous product stream; unreacted hydrocarbon is recycled to the reaction zone and carbon monoxide is recycled to the inlet to or outlet from the hydrocarbon reaction zone.

The hydrocarbon used in the reaction will, of course, depend upon which petrochemical is to be produced. If it is desired to produce a cyclic anhydride, the hydrocarbon will be an aromatic hydrocarbon or a straight chain hydrocarbon. For instance, if it is desired to produce phthalic anhydride, the hydrocarbon feed is preferably o-xylene or naphthalene, and if maleic anhydride is desired, the hydrocarbon feed is generally 91A210/MV IE 913947 7 benzene or straight-chain hydrocarbons containing four carbon atoms (C^ hydrocarbons). Straight-chain hydrocarbons are currently preferred over benzene for the manufacture of maleic anhydride because of the high cost of benzene. The straight-chain hydrocarbons contemplated for use in the invention are n-butane, butene and butadiene. n-Butane is the most preferred hydrocarbon for maleic anhydride manufacture because it is less expensive than the unsaturated hydrocarbons, the latter being more valuable because of their usefulness as monomers. Commercial grade n-butane often contains other hydrocarbons, such as i-butane, but these impurities are not objectionable because they do not interfere with the manufacture of maleic anhydride from n-butane.

On the other hand, if it is desired to produce an unsaturated nitrile, the hydrocarbon is preferably a straight chain saturated or ethlenically unsaturated hydrocarbon. For example, if it is desired to produce methacrylonitrile, the hydrocarbon feed is preferably isobutane or isobutene, and if acrylonitrile is desired, the hydrocarbon feed is generally propane or propylene.

The process of the invention will be described with particular reference to the manufacture of maleic anhydride from n-butane and acrylonitrile from propane, but the invention is not limited thereto.

The oxygen-containing gas may be air, oxygen-enriched air, other oxygen-inert gas mixtures or substantially pure oxygen. By oxygen-enriched air is meant air that contains more oxygen than is naturally present in air. Oxygen-inert gas mixtures include oxygen-nitrogen mixtures, oxygen-argon mixtures, oxygen-carbon dioxide mixtures, etc. Pure oxygen is preferred since its use avoids the introduction of inert gases, such as nitrogen and argon, into the system and the subsequent need to remove excess quantities of these inert gases from the product gas stream to prevent their build-up in the system.

The invention can be better understood from the accompanying drawings, in which the same reference numerals are used to designate the same or similar pieces of equipment in different figures. Auxiliary equipment, including compressors, heat exchangers and valves not necessary for an understanding of the invention, have been omitted from the drawings to 91A210/MW IE 913947 -βsimplify discussion of the invention.

Considering first Fig. 1, the apparatus of this embodiment includes a hydrocarbon partial oxidation reactor 2 having a feed inlet means 4 and a product outlet line 6. Product outlet line 6 is connected to a hydrocarbon derivative recovery unit 8, which may be a condenser or a scrubber which receives a scrubbing liquid through inlet line 10 and discharges a liquid product through outlet line 12. The unit 8 is also equipped with an outlet line 14 for gas depleted of the hydrocarbon derivative which communicates with carbon dioxide separator 16.

Separator 16 is provided with a waste gas discharge line 18, and it is also connected via recycle line 20 with feed inlet means 4. The system of Fig. 1 can also be equipped with a bypass line 22, controlled by valve 24.

Reactor 2 may be any suitable reactor but it is usually of the fixed, moving, fluidised, or transport catalyst bed design. Reactor 2 may be equipped with heat exchange means (not shown) to remove heat developed in the reaction, which is exothermic. The specific design details of suitable reactors are well known and they form no part of the present invention. When product recovery unit 8 is a gas scrubber, i.e. an absorber, it is usually of the packed bed design, and it is here illustrated as equipped with means for spraying water or an aqueous or non-aqueous liquid on the product gas entering this unit from reactor 2. Carbon dioxide separator 16 serves to remove carbon dioxide and other inert gases from the gaseous effluent from the product removal means and this unit can be any device which will accomplish this result. Separator 16 is usually an adsorber, an absorber or a membrane separation unit. In preferred embodiments of the invention, separator 16 is a pressure swing adsorption (PSA) unit or a temperature swing adsorption (TSA) unit.

Fig.2 illustrates a variation of the system of Fig. 1. In the embodiment of Fig. 2, the equipment train includes a hydrocarbon separator 26, and the piping arrangement has been modified. Hydrocarbon separator 26 can be any suitable device that is capable of selectively removing gaseous hydrocarbon from a gas mixture. Suitable separators include adsorbers and absorbers. In preferred embodiments, separator 26 is a PSA unit or a TSA unit. Additional details concerning separators 16 and 26 are 91A210/MW provided below.

In the piping arrangement of Fig. 2, Line 14 connects the outlet from scrubber 8 to the inlet to unreacted hydrocarbon separator 26, line 28 connects the outlet from hydrocarbon separator 26 to the inlet to carbon dioxide separator 16 and recycle line 30 connects hydrocarbon separator 26 to feed inlet means 4. Additionally, bypass line 22, controlled by valve 24, connects line 28 to recycle line 20; bypass line 34, controlled by valve 36, connects recycle line 20 to line 6; and valve 32 controls the rate of flow of fluid through line 20 to inlet means 4.

As indicated above, separators 16 and 26 can be any means for separating the desired component (unreacted hydrocarbon or carbon monoxide or both) from the scrubbed gas stream, but in the most preferred embodiment these devices are pressure swing adsorption units. Pressure swing adsorption is a well known process for separating the components of a mixture of gases by virtue of the difference in the degree of adsorption among them on a particulate adsorbent retained in a stationary bed. Typically, two or more such beds are operated in a cyclic process comprising adsorption under relatively high pressure and desorption or bed regeneration under relatively low pressure or vacuum. The desired component or components may be obtained during either of these stages. The cycle may contain other steps in addition to the fundamental steps of adsorption and regeneration, and it is commonplace to have two or more adsorbent beds cycled 180° out of phase to assure a pseudo continuous flow of desired product. While it is conventional for the adsorption step of a PSA cycle to be carried out under pressure, it can run at ambient pressure with desorption under vacuum.

In the process of the invention practised in the Fig. 1 system, feed, comprising a suitable hydrocarbon, an oxygen-containing gas and the recycle gas stream, enters reactor 2 through inlet means 4, which may comprise a single inlet line through which a mixture of the gaseous reactants and diluents is introduced into reactor 2, or it may comprise several individual inlet lines for separately introducing the reactants into the reactor. The particular inlet arrangement will generally depend upon the type of reactor used for practising the invention. In fixed bed reactor systems the components of the feed are often mixed before they 91A210/MW IE 913947 - ίο enter the reactor and are thus fed into the reactor through a single line, whereas in fluidised bed reactor systems, the components are often separately fed into the reactor.

The feed gases entering reactor 2 contact the catalyst and react to form the product gases. Any of the well known catalysts for oxidising hydrocarbons to the desired petrochemical product under the specified conditions can be used in the process of the invention. For the oxidation of hydrocarbons to cyclic anhydrides, suitable catalysts include vanadia-based catalysts, such as vanadium oxides, vanadium/molybdenum oxides, vanadium/phosphorus oxides and vanadium/titanium oxides. For the ammoxidation of hydrocarbons to nitriles, suitable catalysts include iron-antimony oxides and bismuth-antimony oxides. These catalysts and their use are conventional and well known to those skilled in the manufacture of the desired petrochemical products. The specific hydrocarbon partial oxidation catalysts used in the process of the invention do not form a critical part of the invention.

The conditions of the hydrocarbon partial oxidation are well known and form no part of the invention. Typically, the partial oxidation reaction is conducted at a temperature of from about 250° to 600°C, and usually from about 300° to 500°C, and at low pressures, typically in the range of from about 2 to 50 psig, and usually from about 3 to 30 psig. The reactants are generally passed through the reactor at a velocity in the range of from about 0.5 to 5.0 ft/sec. The ratios of oxygen to hydrocarbon and ammonia to hydrocarbon (in the case of nitrile production) in the feed are suitably in the ranges of about 0.3:1 to 10:1 and about 0.8:1 to 1.3:1 by volume, respectively.

The product gas stream leaving reactor 2 contains the desired petrochemical as the main product, and carbon dioxide and carbon monoxide as by-products. As noted above, the product stream generally also contains unreacted hydrocarbon and oxygen, and may contain small amounts of other by-products, impurity gases and nonreactive hydrocarbons. The product gas stream leaves reactor 2 via line 6 and passes through a heat exchanger (not shown) wherein it is cooled to a temperature in the range of about 30 to about 200°C. The cooled product gas stream enters 91A210/MW IE 913947 - n petrochemical product removal means 8, in which the product is removed from the gas stream. The solvent dissolves substantially all of the petrochemical in the product gas stream and the petrochemical product-containing solution exits scrubber 8 via line 12. It is usually further treated to recover the petrochemical product. The scrubbed gas stream leaves product removal means 8 through line 14 and enters separator 16.

The principal purpose of separator 16 is to prevent the build-up of carbon dioxide and other inert gases in the system. It is preferred to recycle only carbon monoxide and the unreacted hydrocarbon, so that the process can be optimised. Accordingly, if carbon dioxide is not removed, its concentration in the system will increase and may eventually dilute the carbon monoxide concentration to the point at which a flammable mixture exists. To avoid this problem, it is only necessary to remove an amount of carbon dioxide equal to the amount of carbon dioxide produced in reactor 2 in each pass.

Separator 16 also serves the purpose of removing carbon monoxide in excess of the amounts which it is desired to recycle, and other inert gases from the system. Since carbon monoxide is also a by-product of the partial oxidation reaction it is continuously being produced. After equilibrium is reached a quantity of carbon monoxide approximately equal to the quantity produced in the partial oxidation step in each pass is removed by separator 16 to prevent the build-up of carbon monoxide in the system. Other inert gases, such as nitrogen and argon (introduced into the system when air is used as the source of oxygen) are also removed from the system by means of separator 16. In the latter situation, separator 16 can be a single separator or a train of separators. To prevent the build-up of nitrogen and argon in the system when air used as the source of oxygen, it is generally preferred to remove from the system substantially all of the nitrogen and argon entering reactor 2 with the fresh feed.

When the system of Fig. 1 is operated with bypass line 22 closed, the carbon monoxide to be recycled and all of the unreacted hydrocarbon exit separator 16 via recycle line 20 and are returned to the inlet side of reactor 2. In some cases it may be preferable to have part of the gas 91A210/MW IE 913947 - 12 stream leaving petrochemical product removal means 8 bypass separator 16. This can be effected by partially opening valve 24. This alternative is advantageous when it is desired to have all of the carbon monoxide destined for recycle pass through line 22. This permits separator 16 to be operated so that it removes only unreacted hydrocarbon from the stream entering the separator. Partially by-passing separator 16 is most convenient when the oxidant entering reactor 2 is substantially pure oxygen, because the stream passing through line 22 will then be substantially free of inert gases other than carbon dioxide.

The gas mixture at all points in the reaction system is made non-flammable by maintaining the concentration of carbon monoxide in the system sufficiently high to prevent the gas mixture from forming a flammable mixture. In other words, the concentration of carbon monoxide in the system is at a high enough level that the total concentration of fuel (comprising hydrocarbon reactant and carbon monoxide) is always above the UEL for the system. In the reaction systems of the invention, the carbon monoxide is present as the principal gaseous component, i.e. carbon monoxide is present in the reaction system at a concentration greater than any other gaseous component. The carbon monoxide concentration in the system is preferably maintained sufficiently high so that it alone will prevent the gases in any part of the system from forming a flammable mixture. The concentration of carbon monoxide necessary to provide this effect will vary from system to system, but in general, this result will be attained when the carbon monoxide content of the system comprises at least 30 volume percent of the total gases in the system. In the most preferred embodiment of the invention carbon monoxide comprises at least 40 volume percent of the total gases in the system. It is also most preferred to keep the concentration of gases other than carbon monoxide and the reactant gases as low as possible in the system.

The flammability of the gas mixture at any point in the system is dependent upon the temperature of the gas mixture at that point and the relationship is such that an increase in the temperature results in an increase in the flammable range of the gas mixture. As indicated above, the temperature at which the oxidation reaction takes place is generally in the range of about 250 to 600 °C. Thus, ordinarily there would be a 91A210/MW IE 913947 πsignificant hazard of fire or an explosion in the hydrocarbon partial oxidation reactor. It has also been discovered however, that the flammability of the gas mixture in the hydrocarbon reactor is markedly reduced by the presence of the catalyst in the reactor, so that there is actually little danger of a fire or explosion in the reactor.

The product gas stream exiting reactor 2, however, contains little or no catalyst and is still very hot from the partial oxidation reaction; accordingly, there would be a considerable danger that the flammable components in the product gas stream would ignite as they exit or after they exit reactor 2 and before they are cooled, were it not for the high concentration of carbon monoxide in the reactor effluent. Maintaining a high concentration of carbon monoxide throughout the system insulates the entire system from the hazard of a fire or an explosion.

It may sometimes be desirable to maintain maximum protection in the zone just downstream of the hydrocarbon partial oxidation reaction zone while at the same time maximising the rate of flow of reactants through reactor 2. The embodiment illustrated in Fig.2 is particularly adapted to effecting this result. In the process practised in the system of Fig. 2, part or all of the carbon monoxide recycle stream can be introduced into the system at a point downstream of the reaction zone of reactor 2. This alternative is feasible because, as noted above, the oxidation catalyst itself functions as a flame arrestor in the reactor. This embodiment presents the advantage of providing the carbon monoxide at the point where it is most needed, while at the same time allowing a greater flow of reactants through reactor 2, thereby increasing the production capacity of the system. Introducing the carbon monoxide into the reactor product stream not only serves to prevent the product gas mixture from entering into the flammable mixture range, but, because the carbon monoxide is itself cool, also serves to cool the gas mixture.

In the process of the invention as practised in the system of Fig. 2, the gaseous effluent from petrochemical product removal means 8 is treated in hydrocarbon separator 26 to remove substantially all of the unreacted hydrocarbon from the petrochemical product-depleted gas stream and the separated unreacted hydrocarbon is recycled to the inlet end of hydrocarbon partial oxidation reactor 2. Part or all of the 91A210/MW IE 913947 - u hydrocarbon-depleted effluent from the hydrocarbon separator is then treated in separator 16 to remove carbon dioxide and excess carbon monoxide from the stream and the remainder of the stream, now rich in carbon monoxide, exits separator 16 via line 20 and is recycled to either the inlet to the hydrocarbon partial oxidation reactor by opening valve 32 and closing valve 36, or to the downstream side of reactor 2 by opening valve 36 and closing valve 32, or to both locations by opening valve 32 and valve 36. As was the case with the Fig. 1 embodiment, a portion of the scrubbed gas leaving separator 26 can be by-passed around separator 16 via line 22 by opening valve 24.

In the start-up operation of the process of the invention, supplemental carbon monoxide can be initially introduced into the system with the feed or a high carbon dioxide concentration can be initially maintained in the system to insure that the gas mixture is and remains outside of the flammable range. Then, as the concentration of carbon monoxide increases, the supplemental carbon monoxide or the excess carbon dioxide will gradually decrease and be totally eliminated when the system reaches the desired equilibrium state. At this point the carbon monoxide can be easily maintained in the desired range by controlling the amount of carbon monoxide recycled.

It will be appreciated that it is within the scope of the present invention to utilise conventional equipment to monitor and automatically regulate the flow of gases within the system so that it can be fully automated to run continuously in an efficient manner.

An important advantage of the invention is that it permits the hydrocarbon partial oxidation reaction to be conducted using a hydrocarbon feed concentration that may be varied over a wider range while minimising the risk of fire or explosion in the hydrocarbon partial oxidation reactor or associated equipment. Another advantage is that the partial oxidation reaction may be safely conducted without the use of inert gas diluents, such as nitrogen. The process of this invention is also advantageous in its simplicity, ease of operation, low capital and operating costs and substantially reduced flammability potential. The process can be run at a relatively low per pass conversion of the feed hydrocarbon to the desired product to achieve substantially improved 91A210/MW IE 913947 15 selectivity. It will be appreciated that a system that achieves enhanced selectivity, and hence increased overall yield of a desired product, is highly advantageous.

The invention is further illustrated by the following example wherein, unless otherwise indicated, parts, percentages and ratios are on a volume basis.

EXAMPLE I A vapour phase maleic anhydride production run was simulated in a fluidised bed reactor based on the use of a reactor system similar to the system of Fig. 1. The simulated feed to the hydrocarbon reactor comprises the Fresh Feed component and the Recycle Stream component. The reaction is simulated based on the use of a vapour phase hydrocarbon reactor containing a fluidised catalyst bed of vanadium phosphorous oxide and a pressure swing adsorber containing a molecular sieve adsorption bed. The various flow rates and projected results are tabulated in TABLE I.

Fresh Feed Reactor Feed(l) Scrubber Feed PSA Feed Recycle tfaste Moles VolZ Moles Vol X Moles VolZ Moles VolZ Moles VolZ Moles VolZ i-H CN o o 00 <· o CN © d d d CN © m 'J- m CN o © o i—1 ro Γ*» CO O RO d d CN r* < i—1 CO in RO NT o o in «4· i-H r* CO CN o o σ' rH CO σχ CN CO m CO sr co CN o r* m o d © d NT OR RO rH 00 i“H CN CO co o r*«. o © CO 00 tH m m d d σ CO co m 00 i—l Γ* i—1 CO in cn m CM i—l ι—1 © RO o i—l CN o o CO σ> CO 1—1 CN co o r*. © m 00 00 00 m m d o 00 O co < CN RO m RO i—l 1—1 r* σ\ ι—1 RO o o in VO CO co o o o o 00 os m co CN OR © o m i—l CO τ—I d d O' T i—l co i-M OR O' CN 00 CN OR m CO in co •rt CM CM o cn m cn vo CM cn c Φ c o Q. s o υ CN σ\ σ' o o © o o o φ • « • • * • • • r-1 σ' o O' o o © o o © a τ—1 r* o >» i“H a φ 04 OR RO m o © © © © i—l • • • • * « * • w RO σ' OR o o o o o vO 3 o in Γ'- i—l CN co © CL i—t Ό Φ Φ b Φ x: Φ Φ T3 w c a rt Φ nJ nJ u u M 4-» 4J •rt T3 CH 3 Φ >. CQ CQ r-t 43 CM o z-s 1 1 CN CM nJ C © O CM © i—l C •H o z £ < u O 03 s^z 91A210/MW EXAMPLE II A vapour phase acrylonitrile production run was simulated in a fluidised bed reactor based on the use of a reactor system similar to the system of Fig. 1. The simulated feed to the hydrocarbon reactor comprises the Fresh Feed component and the Recycle Stream component. The reaction is simulated based on the use of a vapour phase hydrocarbon reactor containing a fluidised catalyst bed of and a pressure swing adsorber containing a molecular sieve adsorption bed. The various flow rates and projected results are tabulated in TABLE II. «2 o o > > o cc > © > 13 O 3 o o o o << LC o re 3 i-3 re n> a. 3 o 3 ft o 3 Π *< o XJ F H o w O 1—· 3 3 3 Φ CL oq o H· 3 H*· !-<· fl> Φ □ CD (D ft 3 3 I—1· •Ί ft l·-»· n M· Φ R-> 3 »-> -P- t-» h-* VO 03 -P- xj 00 o o o o O O O o xj o • ♦ • • xj o b b b o o © o Ό 00 o xj I—» o o o o o o o o oo vO h-» o o o o o o o o xj Ό -> te I-* 1—‘ Ι-» te N3 F-> re re NJ vO o P- 4S vO o xj xj © o o o Xj xj 00 xj b te VO o b b o 00 VO 00 1—‘ o ts UJ o o © © o o 00 > o o t-* o o b © Os Xj \O tvj Cb PLa> J Cb 4s Os N3 ts I—* oo N3 xj so o re re 00 ts xj h-» h-* Η-» o o vo O' re te te tn N> b b ts JS 1-* re tn tn 00 tn o o o to H* H* te • • • • • • • • • • vO O' xj H* o 00 00 o »-* H* 1—* ts 00 xj re 00 o 1—* 1—» o © © o vO o re • • • • b CD -> b o b o -> o 1—* t-‘ 00 o o te o o o o o -> • • • • • • • • • • o to 4s o o © o xj o xj O' UJ ω vO xj Xj o o o o re o • • • « • • Xl • to 00 o o © o • o Ό sj oo -J Ln UJ UJ o o o o tn xj £* te o o o o Ι-» o • « • • • • • • tn O' o o o o tn o tn O tn o o o o 1-» o • • • • • • • • 00 o o o o o h-* o Fresh Feed Reactor Feed Scrubber Feed PSA Feed Recycle Waste Component Moles VolZ Moles VolZ Moles VolZ Moles VolZ Moles VolZ Moles_VolZ 91A210/MW Although the invention has been described with particular reference to specific experiments, these experiments are merely exemplary of the invention and variations are contemplated. For example, the reaction can be carried out under conditions that will effect the production of other cyclic anhydrides and nitriles. Similarly, other catalysts and adsorbents and other means of gas separation can be used in the invention, if desired. Similarly, the process of the invention may be practised in equipment arrangements other than those illustrated in the drawings.

Claims (15)

1. A process for the production of a hydrocarbon derivative selected from cyclic anhydrides and nitriles comprising: (a) contacting in the vapour phase in a reaction zone a hydrocarbon, an oxygen-containing gas and, if the hydrocarbon derivative is a nitrile, ammonia, in the presence of an partial oxidation catalyst and carbon monoxide as the principal gaseous component under conditions which produce a gaseous product containing said hydrocarbon derivative, carbon monoxide and carbon dioxide; (b) recovering said hydrocarbon derivative from said gaseous product; (c) separating carbon dioxide from the gaseous product; and (d) recycling the carbon dioxide-depleted gaseous product to said reaction zone or its outlet (or both), the concentration of carbon monoxide and hydrocarbon present in all parts of the system in which said process is conducted being maintained sufficiently high during said process to prevent the existence of a flammable mixture in said system.

2. A process according to Claim 1, wherein said cyclic anhydride is maleic anhydride and said hydrocarbon is a straight-chain hydrocarbon containing four carbon atoms.

3. A process according to Claim 2, wherein said straight-chain hydrocarbon containing four carbon atoms is n-butane.

4. A process according to Claim 1, wherein said cyclic anhydride is phthalic anhydride and said hydrocarbon is ortho-xylene.

5. A process according to Claim 1, wherein said nitrile is acrylonitrile, and said hydrocarbon is propane or propylene or a mixture of both propane and propylene.

6. A process according to Claim 1, wherein said nitrile is isobutane or isobutene or a mixture of both isobutane and isobutene. 91A210/MW IE 913947 -η

7. A process according to any one of the preceding claims, in which the carbon dioxide is separated from said gaseous product by pressure swing adsorption.

8. A process according to any one of the preceding claims, in which the concentration of carbon monoxide throughout the system exceeds 40% by volume.

9. A process according to any one of the preceding claims, wherein said oxygen-containing gas is substantially pure oxygen.

10. A process according to any one of the preceding claims, in which unreacted hydrocarbons are separated from said gaseous product upstream of the separation of the carbon dioxide and are recycled to the said reaction zone.

11. Apparatus for producing a hydrocarbon derivative by the vapour phase partial oxidation of a hydrocarbon with oxygen in the presence of an partial oxidation catalyst comprising: (a) reactor means for oxidising a hydrocarbon with oxygen to produce a gaseous product stream containing said hydrocarbon derivative, carbon monoxide and unreacted hydrocarbon; (b) means for removing hydrocarbon derivative from said gaseous product stream to produce a liquid product stream containing said hydrocarbon derivative and a gas stream, substantially free of said hydrocarbon derivative, containing carbon monoxide and unreacted hydrocarbon; (c) means for separately removing unreacted hydrocarbon and carbon monoxide from said gas stream; (d) means for recycling said separated unreacted hydrocarbon to the upstream side of said reactor means; and (e) means for recycling said separated carbon monoxide to the downstream side of said reactor means. - 22

12. A process for the production of a hydrocarbon derivative substantially as described herein with reference to the accompanying drawings.

13. A process for the production of a hydrocarbon derivative substantially as described herein by way of Example.

14. Apparatus for producing a hydrocarbon derivative substantially as described herein with reference to the accompanying drawings.

15. Hydrocarbon derivatives prepared by the method of any of Claims 1 to 10, 12 and 13 or using the apparatus of Claim 11 or Claim 14.